Due to the relatively poor cell-material interaction of alginate hydrogel, alginate-gelatin crosslinked (ADA-GEL) hydrogel was synthesized through covalent crosslinking of alginate di-aldehyde (ADA) ...with gelatin that supported cell attachment, spreading and proliferation. This study highlights the evaluation of the physico-chemical properties of synthesized ADA-GEL hydrogels of different compositions compared to alginate in the form of films. Moreover, in vitro cell-material interaction on ADA-GEL hydrogels of different compositions compared to alginate was investigated by using normal human dermal fibroblasts. Viability, attachment, spreading and proliferation of fibroblasts were significantly increased on ADA-GEL hydrogels compared to alginate. Moreover, in vitro cytocompatibility of ADA-GEL hydrogels was found to be increased with increasing gelatin content. These findings indicate that ADA-GEL hydrogel is a promising material for the biomedical applications in tissue-engineering and regeneration.
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Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The miscible amorphous/semi-crystalline polymer blends with shape memory potential has received increasing interests in recent years. In this work, the shape memory mechanism of the miscible ...amorphous PMMA/semi-crystalline PLA blends was investigated using thermo-mechanical and rheological approaches. With the incorporation of PMMA into PLA, a broad glass transition and increased glass transition temperature Tg were observed by differential scanning calorimetry (DSC) measurements. The broadening of glass transition is attributed to the local nanoscale heterogeneities in the miscible blend system which is related to the self-concentration of the components. The degree of molecular entanglement of the blends was derived based on the oscillatory rheological measurements, showing that the dissimilar chains are more likely to entangle with each other than the similar ones, and the entanglement density ve is enhanced with increased PMMA content up to 50% where a 100% recovery of the initial shape is yielded. After that, ve is reduced with the addition of PMMA. The mechanism underlying the shape memory property is further validated by performing the shape memory test on the PLA/PMMA blend films at respective Tg. It is evident that for the semi-crystalline blends (PLA rich), PLA crystallites and molecular entanglement provide physical cross-links for shape recording, while a negative effect of crystallinity on the shape recovery ratio is obtained due to the strain-induced crystallization and chain slippage between the crystalline and amorphous chains. In contrast, for the amorphous blends (PMMA rich), the shape recovery ratio shows a strong positive linear dependence on ve, and the entanglement network is regard as the most important factor in the shape memory performance.
Average entanglement molar mass Me, Me,PLA-PMMA and entanglement density of ve PLA/PMMA blends versus composition. Display omitted
•The shape memory mechanism of miscible amorphous/semicrystalline polymer blends is studied.•Entanglement network could be formed in the PLA/PMMA blends.•The dissimilar chains are more likely to entangle with each other than the similar ones.•Entanglement network and crystallites are responsible for the shape memory performance.
Microencapsulation of cells by using biodegradable hydrogels offers numerous attractive features for a variety of biomedical applications including tissue engineering. This study highlights the ...fabrication of microcapsules from an alginate-gelatin crosslinked hydrogel (ADA-GEL) and presents the evaluation of the physico-chemical properties of the new microcapsules which are relevant for designing suitable microcapsules for tissue engineering. Alginate di-aldehyde (ADA) was synthesized by periodate oxidation of alginate which facilitates crosslinking with gelatin through Schiff's base formation between the free amino groups of gelatin and the available aldehyde groups of ADA. Formation of Schiff's base in ADA-GEL and aldehyde groups in ADA was confirmed by FTIR and NMR spectroscopy, respectively. Thermal degradation behavior of films and microcapsules fabricated from alginate, ADA and ADA-GEL was dependent on the hydrogel composition. The gelation time of ADA-GEL was found to decrease with increasing gelatin content. The swelling ratio of ADA-GEL microcapsules of all compositions was significantly decreased, whereas the degradability was found to increase with the increase of gelatin ratio. The surface morphology of the ADA-GEL microcapsules was totally different from that of alginate and ADA microcapsules, observed by SEM. Two different buffer solutions (with and without calcium salt) have an influence on the stability of microcapsules which had a significant effect on the gelatin release profile of ADA-GEL microcapsules in these two buffer solutions.
Many different biofabrication approaches as well as a variety of bioinks have been developed by researchers working in the field of tissue engineering. A main challenge for bioinks often remains the ...difficulty to achieve shape fidelity after printing. In order to overcome this issue, a homogeneous pre-crosslinking technique, which is universally applicable to all alginate-based materials, was developed. In this study, the Young's Modulus after post-crosslinking of selected hydrogels, as well as the chemical characterization of alginate in terms of M/G ratio and molecular weight, were determined. With our technique it was possible to markedly enhance the printability of a 2% (w/v) alginate solution, without using a higher polymer content, fillers or support structures. 3D porous scaffolds with a height of around 5 mm were printed. Furthermore, the rheological behavior of different pre-crosslinking degrees was studied. Shear forces on cells as well as the flow profile of the bioink inside the printing nozzle during the process were estimated. A high cell viability of printed NIH/3T3 cells embedded in the novel bioink of more than 85% over a time period of two weeks could be observed.
The crystallinity of polymers is usually determined via Differential Scanning Calorimetry (DSC), X-ray diffraction (XRD) or density measurements. Even though DSC is an easy and fast way to determine ...crystallinity, it suffers of several disadvantages in the case of fibers and nonwovens. In DSC studies, the sample preparation of fiber material may be difficult, results are not calibration free and heat is introduced in the measuring process, which might lead to transitions in instable crystal structures in the polymer. XRD is able to overcome these problems but is also time consuming and complicated in terms of sample preparation and evaluation of the measurements. Furthermore, it is not possible to determine surface crystallinity or crystallinity gradients inside the specimen with both methods.
Based on approaches found in literature, a method was developed which is capable of measuring the degree of crystallinity in the bulk and at the surface of Polypropylene via Fourier transformed infrared spectroscopy. A broad set of calibration samples with a wide range of degrees of crystallinity but without a crystallinity gradient was produced by cooling samples with cooling rates from 1 to 3500 K min−1. The degree of crystallinity was then determined from the ratio of the maximum peak height at 974 cm−1 and the maximum peak height at 998 cm−1 multiplied by 61.4%.
Consecutively, the transferability of the method to the measurement of fibers and nonwovens is demonstrated and verified via procedures which are already well described in literature. This method has an excellent reproducibility, spatial resolution and is capable of determining the degree of crystallinity in less than 5 min. Furthermore, this method is easy to implement and does not require further sample preparation.
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•Development of a method, which is able to measure surface and bulk crystallinity of Polypropylene.•Method is capable of measuring surface and bulk crystallinity of fibers in a non-destructive, location-sensitive and fast way.•Surface and bulk crystallinity of fibers and nonwovens produced under different processing conditions is determined.•Influence of the calendaring process on bonding points and fibers spun from the melt is shown.•Influence of storage time and temperature on fiber crystallinity and post-crystallization is revealed.
Due to the lack of raw material and forced by political demand, an increasing percentage of postconsumer materials (PCR) shall be used in all processing methods in polymer technology. Thermoforming, ...as one of the oldest polymer-processing methods, has special requirements regarding the melt stability at high temperatures. Low melt stability affects the thermoforming in a negative manner, as the low stiffness leads the sheet to sag during the heating phase. In this study, two-layer sheets are used in order to improve melt stability of PCR material. The focus is placed on the influence of rheological properties on the biaxial stretching behavior of mono- and two-layer sheets in partially molted state. In order to create a stabilizing layer, two different thermoformable virgin materials with a melt flow rate (MFR) of 3 g/10 min and 6 g/10 min were chosen. The second layer consists of instable PCR materials with a MFR of 16 g/10min and 50 g/10 min. Rheological investigations, molecular characterization and biaxial stretching tests are used to show the benefit of two-layer sheets for processing PCR material under elongational stress. The results show that the use of two-layer sheets can improve the biaxial stretching properties, so that two-layer sheets can offer a significant potential in the processing of PCR materials in thermoforming.
Aerosol deposition is a feasible method of fabricating dense ceramic films at room temperature by the impact consolidation of submicron‐sized particles on ceramic, metal, glass, and polymer ...substrates at a rapid rate. Despite the potential usefulness of the aerosol deposition process, there are issues, such as deposition mechanisms and structure of the film‐substrate interface, that are not well understood. We have used complementary structural and microstructural analysis to capture the state of the substrate surface after the aerosol deposition process. The results reveal that modification of the substrate surface by the ejected submicron‐sized particles is essential for the formation of anchoring layer, thereby, a change in internal residual stress state and surface free energy of the substrate is required to deposit film using AD process. Our analysis also suggests that the adhesion between the metal substrate and ceramic particles is possibly contributed by both physical bonding and mechanical interlocking.
Steps involved for investigation of the effect of AD processing at the substrate interface using NaCl coating.
Understanding of the physical characteristics of a polymer requires molar mass determination. For the commercially available polymers, having average molar mass below 1 000 000 g/mol, chromatography ...is the method that is often applied to determine the molar mass and molar mass distribution. However, the application of conventional chromatography techniques for polymers having molar mass >1 000 000 g/mol becomes very challenging, and often the results are disputed. In this article, melt rheometry based on the “modulus model” is utilized to measure the molar mass and polydispersity of ultra high-molecular-weight polyethylenes (UHMWPEs) having molar mass >1 000 000 g/mol. Results are compared with the chromatography data of the same polymer samples and the boundary conditions where the chromatography technique fails, whereas the rheometry provides the desired information is discussed. The rheological method is based on converting the relaxation spectrum from the time domain to the molecular weight domain and then using a regularized integral inversion to recover the molecular weight distribution curve. The method is of relevance in determining very high molar masses (exceeding 3 000 000 g/mol) that cannot be ascertained conclusively with the existing chromatography techniques. For this study, UHMWPEs with various weight-average molar masses, where the number-average molar mass exceeds >1 000 000 g/mol, are synthesized. Catalyst used for the synthesis is a living homogeneous catalyst system: MAO-activated bis(phenoxy imine) titanium dichloride. The rheological behavior of the thus synthesized nascent reactor powders confirms the disentangled state of the polymer that tends to entangle with time in melt.
Thermoplastic Polyurethane (TPU) is a unique tailorable material due to the interactions of hard and soft segments within the block-copolymer chain. Therefore, various products can be created out of ...this material. A general trend towards a circular economy with regards to sustainability in combination with TPU being comparably expensive is of high interest to recycle production as well as post-consumer wastes. A systematic study investigating the property changes of TPU is provided, focusing on two major aspects. The first aspect focuses on characterizing the change of basic raw material properties through recycling. Gel permeation chromatography (GPC) and processing load during extrusion indicate a decrease in molar mass and consequently viscosity with an increasing number of recycling cycles. This leads to a change in morphology at lower molar mass, characterized by differential scanning calorimetry (DSC) and visualized by atomic force microscope (AFM). The change in molar mass and morphology with increasing number of recycling cycles has an impact on the material performance under tensile stress. The second aspect describes processing of the recycled TPU to nonwoven fabrics utilizing melt blowing, which are evaluated with respect to relevant mechanical properties and related to molecular characteristics. The molar mass turns out to be the governing factor regarding mechanical performance and processing conditions for melt blown products.
Within this contribution, the effect of grinding media wear on the melt crystallisation of polybutylene terephthalate (PBT) is addressed. PBT was wet ground in a stirred media mill in ethanol using ...different grinding media beads (silica, chrome steel, cerium-stabilised and yttrium-stabilised zirconia) at comparable stress energies with the intention to use the obtained particles as feed materials for the production of feedstocks for laser powder bed fusion additive manufacturing (PBF-AM). In PBF‑AM, the feedstock's optical, rheological and especially thermal properties-including melt crystallisation kinetics-strongly influence the processability and properties of the manufactured parts. The influence of process parameters and used grinding media during wet comminution on the optical properties, crystal structure, molar mass distribution, inorganic content (wear) and thermal properties of the obtained powders is discussed. A grinding media-dependent acceleration of the melt crystallisation could be attributed to wear particles serving as nuclei for heterogeneous crystallisation. Yttrium-stabilised zirconia grinding beads proved to be the most suitable for the production of polymer powders for the PBF process in terms of (fast) comminution kinetics, unchanged optical properties and the least accelerated crystallisation kinetics.
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